Method of making a cured composition

Abstract

This invention relates to a method for preparing a cured composition.

Description

Invention Field

[0001] This invention relates to methods for preparing curing compositions, curing compositions, layers, color conversion devices, uses of color conversion devices, and optical devices. Background Technology

[0002] WO 2017 / 054898 A1 describes a composition comprising red emitting nanocrystals, a wetting agent and a dispersant, propylene glycol monomethyl ether acetate as a solvent, and a mixture of acrylic polymers including acrylic units containing acid groups and silane-modified acrylic units.

[0003] WO 2019 / 002239 A1 discloses a composition comprising semiconductor light-emitting nanoparticles, a polymer, and (meth)acrylates, such as 1,4-cyclohexanediethanol-monoacrylate with a high viscosity of about 90 cp.

[0004] Patent documents

[0005] 1.WO 2017 / 054898 A1

[0006] 2.WO 2019 / 002239 A1 Invention Overview

[0008] However, the inventors have recently discovered that one or more important issues still need to be addressed, as listed below.

[0009] TiO2 particles, typically used as scattering particles in QD inks, have a fairly high density, and combined with the relatively large particle size required for effective visible light scattering, sedimentation is a common problem. Sedimentation, often caused by aggregation, leads to problems in the inkjet printing process. Therefore, there is a desire to develop an ink that typically requires less TiO2 or no scattering particles to achieve high EQE.

[0010] Furthermore, the addition of TiO2 leads to a significant increase in viscosity. Therefore, it is desirable to provide QD inks that typically have less or no TiO2 or scattering particles, which would thus provide greater flexibility in ink design as well as the selection and concentration of other ink components.

[0011] The benefits of this invention are that, compared to reference inks, it achieves higher EQE and lower BL for QD inks with no or fewer scattering particles, higher haze values ​​for cured QD inks with no or fewer scattering particles, and simultaneously achieves higher haze values ​​and higher EQE for cured QD inks with no or fewer scattering particles, while potentially achieving lower blue light leakage.

[0012] A novel method is desired to prepare cured compositions with higher EQE, lower blue light leakage, shorter processing time, improved post-curing haze, improved curing to polymerize the composition, and / or to achieve lower viscosity of the composition.

[0013] The goal is to find the optimal amount of luminescent components and scattering particles in the composition to achieve a composition with low viscosity, high EQE, low blue light leakage, and good inkjet performance.

[0014] The inventors aim to solve one or more of the above-mentioned problems.

[0015] Then a new method for preparing the cured composition was discovered, which includes at least the following steps:

[0016] a) Using light to irradiate the composition as the first light irradiation;

[0017] b) Using the light-irradiated composition as a second light irradiation;

[0018] The composition comprises at least one luminescent portion and a reactive monomer, preferably the monomer having one or more functional groups, more preferably (meth)acrylate monomer;

[0019] The intensity of the light irradiated by the first light and the intensity of the light irradiated by the second light satisfy the following formula (I).

[0020] The intensity of the light illuminating the first ray is less than the intensity of the light illuminating the second ray. (I)

[0021] In another aspect, the present invention also relates to cured compositions obtained or available by the methods of the present invention.

[0022] In another aspect, the present invention also relates to layers obtained or available by the method of the present invention.

[0023] In another aspect, the present invention also relates to a layer comprising a light-emitting portion, a matrix material, and scattering particles, wherein, based on the total amount of the layer, the total amount of the light-emitting portion ranges from 0.1 wt% to 90 wt%, more preferably from 10 wt% to 70 wt%, and even more preferably from 30 wt% to 50 wt%; and

[0024] Based on the total amount of the layer, the total amount of the scattering particles is 10% by weight or less, preferably in the range of 5% to 1% by weight, more preferably in the range of 4% to 2% by weight, preferably the layer is configured to achieve an EQE value of 20% or greater, more preferably the EQE value is in the range of 20% to 99%, more preferably the EQE value is in the range of 30% to 50%, and even more preferably the EQE value is in the range of 30% to 40%. For blue-green conversion efficiency, preferably the layer is a patterned layer.

[0025] On the other hand, the present invention also relates to a color conversion device (100) comprising at least a first pixel (161) which is partially or completely filled with the cured composition of the present invention or filled with any of the layers of the present invention, and a dam (150) comprising at least a polymer material, preferably, the color conversion device (100) further comprising a support medium (170).

[0026] In another aspect, the present invention relates to the use of a color conversion device (100) in an optical device (300) comprising at least one functional medium (320, 420, 520) configured to modulate light or to emit light.

[0027] Furthermore, in another aspect, the present invention relates to an optical device (300) comprising at least one functional medium (320, 420, 520) configured to modulate light or configured to emit light, and a color conversion device (100) of the present invention.

[0028] Other advantages of the invention will become apparent from the following detailed description.

[0029] Attached Figure Description

[0030] Figure 1 A schematic cross-sectional view of one embodiment of the color conversion film (100) is shown.

[0031] Figure 2 A top view showing a schematic diagram of another embodiment of the color conversion film (100) of the present invention is shown.

[0032] Figure 3 A cross-sectional view of a schematic diagram of one embodiment of the optical device (300) of the present invention is shown.

[0033] Figure 4 A cross-sectional view of a schematic diagram of another embodiment of the optical device (300) of the present invention is shown.

[0034] Figure 5 A cross-sectional view of a schematic diagram of another embodiment of the optical device (300) of the present invention is shown.

[0035] Figure 6 The EQE measurement results of working example 12 are shown.

[0036] Figure 7 The blue light leakage measurement results of Working Example 12 are shown.

[0037] Figure 8 The EQE measurement results for Working Example 14 are shown.

[0038] Figure 9 The EQE measurement results for Working Example 14 are shown.

[0039] Figure 10 Viscosity measurement results for Working Example 15 are shown.

[0040] Figure 11 Viscosity measurement results for Working Example 15 are shown.

[0041] Figure 1 List of reference numerals in the attached figures

[0042] 100. Color conversion device

[0043] 110. Light-emitting part

[0044] 110R. Illuminated part (red)

[0045] 110G. Illuminating part (green)

[0046] 120. Matrix material

[0047] 130. Light scattering particles (optional)

[0048] 140. Colorant (optional)

[0049] 140R. Colorant (Red) (Optional)

[0050] 140g. Colorant (green) (optional)

[0051] 140B. Colorant (blue) (optional)

[0052] 150.Dike

[0053] 161. First pixel

[0054] 162. Second pixel

[0055] 163. Third pixel

[0056] 170. Support medium (substrate) (optional)

[0057] Figure 2 List of reference numerals in the attached figures

[0058] 200. Color conversion film

[0059] 210R pixels (red)

[0060] 210G pixels (green)

[0061] 210 pixels (blue)

[0062] 220.Dike

[0063] Figure 3 List of reference numerals in the attached figures

[0064] 300. Optical devices

[0065] 100. Color conversion device

[0066] 110. Light-emitting part

[0067] 110R. Illuminated part (red)

[0068] 110G. Illuminating part (green)

[0069] 120. Matrix material

[0070] 130. Light scattering particles (optional)

[0071] 140. Colorant (optional)

[0072] 140R. Colorant (Red) (Optional)

[0073] 140g. Colorant (green) (optional)

[0074] 140B. Colorant (blue) (optional)

[0075] 150.Dike

[0076] 320. Optical modulator

[0077] 321. Polarizer

[0078] 322. Electrode

[0079] 323. Liquid crystal layer

[0080] 330. Light source

[0081] 331. LED light source

[0082] 332. Optical guide plate (optional)

[0083] 333. Light emitted from the light source (330)

[0084] Figure 4 List of reference numerals in the attached figures

[0085] 400. Optical devices

[0086] 100. Color conversion device

[0087] 110. Light-emitting part

[0088] 110R. Illuminated part (red)

[0089] 110G. Illuminating part (green)

[0090] 120. Matrix material

[0091] 130. Light scattering particles (optional)

[0092] 140. Colorant (optional)

[0093] 140R. Colorant (Red) (Optional)

[0094] 140g. Colorant (green) (optional)

[0095] 140B. Colorant (blue) (optional)

[0096] 150.Dike

[0097] 420. Optical modulator

[0098] 421. Polarizer

[0099] 422. Electrode

[0100] 423. Liquid Crystal Layer

[0101] 430. Light source

[0102] 431. LED light source

[0103] 432. Optical guide plate (optional)

[0104] 440. Color Filter

[0105] 433. Light emitted from the light source (330)

[0106] Figure 5 List of reference numerals in the attached figures

[0107] 500. Optical devices

[0108] 100. Color conversion device

[0109] 110. Light-emitting part

[0110] 110R. Illuminated part (red)

[0111] 110G. Illuminating part (green)

[0112] 120. Matrix material

[0113] 130. Light scattering particles (optional)

[0114] 140. Colorant (optional)

[0115] 140R. Colorant (Red) (Optional)

[0116] 140g. Colorant (green) (optional)

[0117] 140B. Colorant (blue) (optional)

[0118] 150.Dike

[0119] 520. Light-emitting devices (e.g., OLEDs)

[0120] 521.TFT

[0121] 522. Electrode (Anode)

[0122] 523. Base

[0123] 524. Electrode (Cathode)

[0124] 525. Emitting layer (e.g., one or more OLED layers)

[0125] 526. Light emitted from the light-emitting device (520)

[0126] 530. Optical layer (e.g., polarizer) (optional)

[0127] 540. Color Filter

[0128] Terminology Definition

[0129] In this specification, unless otherwise stated, symbols, units, abbreviations and terms have the following meanings.

[0130] In this specification, unless otherwise specifically stated, the singular form includes the plural form, and "a" or "that" means "at least one". In this specification, unless otherwise specifically stated, the elements of a concept may be represented by multiple substances, and when describing quantities (e.g., mass% or mole%), it refers to the sum of multiple substances. "And / or" includes combinations of all elements, and also includes the individual use of elements.

[0131] In this specification, when “to” or “-” is used to indicate a range of values, it includes the endpoints and the units are shared. For example, 5 to 25 mol% means 5 mol% or more and 25 mol% or less.

[0132] In this specification, hydrocarbon refers to a substance comprising carbon and hydrogen, and optionally including oxygen or nitrogen. A hydrocarbon group refers to a hydrocarbon with a monovalent, divalent, or higher valence. In this specification, aliphatic hydrocarbon refers to a straight-chain, branched, or cyclic aliphatic hydrocarbon, and an aliphatic hydrocarbon group refers to an aliphatic hydrocarbon with a monovalent, divalent, or higher valence. Aromatic hydrocarbon refers to a hydrocarbon containing an aromatic ring, which may optionally contain not only an aliphatic hydrocarbon group as a substituent but also be condensed with an alicyclic ring. An aromatic hydrocarbon group refers to an aromatic hydrocarbon with a monovalent, divalent, or higher valence. Furthermore, an aromatic ring refers to a hydrocarbon containing a conjugated unsaturated ring structure, and an aliphatic ring refers to a hydrocarbon having a ring structure but not containing a conjugated unsaturated ring structure.

[0133] In this specification, alkyl means a group obtained by removing any hydrogen from a straight-chain or branched saturated hydrocarbon, including straight-chain alkyl and branched alkyl, and cycloalkyl means a group obtained by removing one hydrogen from a saturated hydrocarbon containing a cyclic structure, optionally including a straight-chain or branched alkyl as a side chain in the cyclic structure.

[0134] In this specification, aryl refers to a group obtained by removing any one hydrogen atom from an aromatic hydrocarbon. Alkylene refers to a group obtained by removing any two hydrogen atom from a straight-chain or branched saturated hydrocarbon. Arylene refers to a hydrocarbon group obtained by removing any two hydrogen atom from an aromatic hydrocarbon.

[0135] In this specification, when the polymer has multiple types of repeating units, these repeating units are copolymerized. These copolymers are any of alternating copolymers, random copolymers, block copolymers, graft copolymers, or any combination of these copolymers.

[0136] According to the present invention, the term "(meth)acrylate polymer" refers to a methacrylate polymer, an acrylate polymer, or a combination of a methacrylate polymer and an acrylate polymer.

[0137] The term "emission" refers to the emission of electromagnetic waves generated by the transition of electrons in atoms and molecules.

[0138] In this instruction manual, Celsius is used as a unit of temperature. For example, 20 degrees means 20 degrees Celsius. Invention Details

[0140] -method

[0141] According to the present invention, a method for preparing a cured composition includes at least the following steps:

[0142] a) Using light to irradiate the composition as the first light irradiation;

[0143] b) Using the light-irradiated composition as a second light irradiation;

[0144] The composition comprises at least one luminescent component and a reactive monomer, preferably the monomer having one or more functional groups, more preferably (meth)acrylate monomer;

[0145] The intensity of the light irradiated by the first light and the intensity of the light irradiated by the second light satisfy the following formula (I).

[0146] The intensity of the light illuminating the first ray is less than the intensity of the light illuminating the second ray. (I)

[0147] In this patent application, it is referred to as a "two-step curing method".

[0148] It is believed that by applying the aforementioned "two-step curing method," the reaction conditions of the composition, including the reactive monomers and the luminescent components, can be well controlled, and the process time can be shortened and optimized. This then results in a higher EQE value for the cured composition (film), lower blue light leakage, and / or improved haze.

[0149] In a preferred embodiment of the invention, the peak wavelengths of the light irradiated by the first light and the peak wavelengths of the light irradiated by the second light are independently within the range of 200 to 450 nm, preferably 365 to 410 nm, and more preferably 375 to 405 nm. Such peak wavelengths are considered preferred wavelengths for smooth curing of the composition.

[0150] In a preferred embodiment of the present invention, the irradiation time of the first light irradiation in step a) is in the range of 1 second to 500 seconds, and the irradiation time of the second light irradiation in step b) is in the range of 1 second to 500 seconds. Preferably, the irradiation time of the first light irradiation in step a) is in the range of 2 seconds to 100 seconds, and the irradiation time of the second light irradiation in step b) is in the range of 2 seconds to 100 seconds. More preferably, the irradiation time of the first light irradiation in step a) is in the range of 3 seconds to 50 seconds, and the irradiation time of the second light irradiation in step b) is in the range of 5 seconds to 50 seconds. Even more preferably, the irradiation time of the first light irradiation in step a) is in the range of 4 seconds to 20 seconds, and the irradiation time of the second light irradiation in step b) is in the range of 7 seconds to 20 seconds.

[0151] It is believed that the composition begins to polymerize upon application of the first light irradiation. The intensity of the first light irradiation is weaker than that of the second light irradiation. Therefore, the composition can polymerize mildly under gentler curing conditions. Then, by applying the second light irradiation with a stronger light intensity, the composition can polymerize well. This results in a higher EQE value and lower blue light leakage in the cured composition. Furthermore, by applying the two-step curing method, the process time can be freely controlled, and a shorter process time can be achieved.

[0152] In a preferred embodiment of the invention, the intensity of the light irradiated by the first light in step (a) is 0.1 mW / cm². 2 Up to 20 mW / cm 2 Within the range, the intensity of the light irradiated by the second light in step (b) is 20 mW / cm². 2 Up to 100 W / cm 2 Within the specified range, preferably, the intensity of the light irradiated by the first light in step (a) is within 0.5 mW / cm². 2 Up to 10 mW / cm 2 Within the range, the intensity of the light irradiated by the second light in step (b) is 100 mW / cm².2 Up to 10 W / cm 2 More preferably, the intensity of the light irradiated by the first light in step (a) is within the range of 1 mW / cm². 2 Up to 5 mW / cm 2 Within the range, the intensity of the light irradiated by the second light in step (b) is 200 mW / cm². 2 Up to 5 W / cm 2 Within the range.

[0153] It is believed that by selecting the aforementioned light intensity, improved EQE values, lower blue light leakage, optimized shorter process times, and well-polymerized cured films (compositions) can be achieved.

[0154] From the viewpoint of achieving a higher EQE, it is suitable to irradiate the composition with light of lower intensity until the composition polymerizes. Preferably, the total energy of the light irradiation is 900 mJ / cm². 2 Up to 5 J / cm 2 Within the range. More preferably, about 2-3 J / cm. 2 .

[0155] In a preferred embodiment of the invention, the composition comprises a variety of light-emitting portions, and based on the total amount of the composition, the total amount of light-emitting portions is preferably in the range of 0.1% to 90% by weight, more preferably 10% to 70% by weight, and even more preferably 30% to 50% by weight.

[0156] In a preferred embodiment of the invention, the composition comprises scattering particles, wherein the total amount of scattering particles is 10% by weight or less, preferably 10% to 0% by weight, more preferably in the range of 5% to 1% by weight, and even more preferably in the range of 4% to 2% by weight, based on the total solid content of the composition.

[0157] It is believed that the above range is preferred from the viewpoint of suitable viscosity of the composition, good dispersibility of scattering particles, high EQE value and / or improved haze value after curing, especially for inkjet printing.

[0158] On the other hand, from the viewpoint of achieving further improved EQE and haze values ​​for the cured film / composition, it is also possible to apply only the first light irradiation without using the "two-step curing method." In this case, no second irradiation step is applied to the composition. The first light irradiation is applied until the composition cures at the aforementioned lower intensity.

[0159] In this case, the intensity of the light irradiated by the first light in step (a) is 0.1 mW / cm². 2 Up to 20 mW / cm 2Within the range, and without second light irradiation, preferably the intensity of the first light irradiation in step (a) is 0.5 mW / cm². 2 Up to 10 mW / cm 2 Within the range, the intensity of the light irradiated by the first light in step (a) is more preferably 1 mW / cm. 2 Up to 5 mW / cm 2 Within the range.

[0160] Preferably, the total energy of the light irradiation is 900 mJ / cm². 2 Up to 5 J / cm 2 Within the range. More preferably about 2-3 J / cm 2 .

[0161] -Reactive monomers

[0162] According to the present invention, the composition for the method comprises at least one reactive monomer, preferably the monomer comprising one or more functional groups, more preferably (meth)acrylate monomers.

[0163] In a preferred embodiment of the present invention, the (meth)acrylate monomer is selected from mono(meth)acrylate monomers, di(meth)acrylate monomers, or tri(meth)acrylate monomers; more preferably, it is a di-methacrylate monomer or a di-acrylate monomer, a tri-methacrylate monomer, or a tri-acrylate monomer; even more preferably, it is represented by the following chemical formula (I).

[0164] (I)

[0165] in

[0166] X 1 It is an unsubstituted or substituted alkyl, aryl, alkoxy, or ester group;

[0167] X 2 It is an unsubstituted or substituted alkyl, aryl, alkoxy, or ester group;

[0168] R 1 It is a hydrogen atom, a halogen atom that is Cl, Br or F, a methyl, alkyl, aryl, alkoxy, ester or carboxylic acid group;

[0169] R 2 It is a hydrogen atom, a halogen atom that is Cl, Br or F, a methyl, alkyl, aryl, alkoxy, ester or carboxylic acid group;

[0170] Preferably, the symbol X 1 yes ,

[0171] In this equation, the "*" on the left side indicates the terminal base C=CR of equation (I).1 The carbon atom connection point, the "*" on the right indicates the symbol X in formula (I). 2 The connection point;

[0172] n is 0 or 1;

[0173] Preferably, the symbol X 2 yes ,

[0174] In this context, the asterisk (*) on the left-hand side of the equation represents the symbol X in equation (I). 1 The connection point, the "*" on the right indicates the connection with the end base C=CR of equation (I). 2 The connection point;

[0175] m is 0 or 1;

[0176] Preferably, at least m or n is 1;

[0177] R 3 It is a straight-chain alkylene or alkoxide having 1 to 25 carbon atoms, a cycloalkyl having 3 to 25 carbon atoms, or an aryl having 3 to 25 carbon atoms, preferably R. 3 It is a straight-chain alkylene or alkeneoxy group having 1 to 15 carbon atoms, more preferably 1 to 5 carbon atoms.

[0178] It can be generated by one or more groups R a Substitution, wherein one or more non-adjacent CH2 groups can be replaced by R a C=CR a C≡C, Si(R) a )2、Ge(R a )2、Sn(R a 2. C=O, C=S, C=Se, C=NR a P(=O)(R) a SO, SO2, NR a OS or CONR a The substitution is possible, and one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2;

[0179] R 4 It is a straight-chain alkylene or alkoxide having 1 to 25 carbon atoms, a cycloalkyl having 3 to 25 carbon atoms, or an aryl having 3 to 25 carbon atoms, preferably R. 4 It is a straight-chain alkylene or alkeneoxy group having 1 to 15 carbon atoms, more preferably 1 to 5 carbon atoms.

[0180] It can be generated by one or more groups R a Substitution, wherein one or more non-adjacent CH2 groups can be replaced by R a C=CRa C≡C, Si(R) a )2、Ge(R a )2、Sn(R a 2. C=O, C=S, C=Se, C=NR a P(=O)(R) a SO, SO2, NR a OS or CONR a The substitution is possible, and one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2;

[0181] R a Each time it appears, it is the same or different of H, D, or an alkyl group having 1 to 20 carbon atoms, a cycloalkyl or alkoxy group having 3 to 40 carbon atoms, an aromatic ring system having 5 to 60 ring carbon atoms, or a heteroaromatic ring system having 5 to 60 carbon atoms, wherein the H atom can be replaced by D, F, Cl, Br, I; two or more adjacent substituents R a They can also form monocyclic or polycyclic, aliphatic, aromatic or heterocyclic ring systems with each other.

[0182] In a preferred embodiment of the invention, the viscosity of the composition is 35 cP or lower at room temperature, preferably in the range of 1 to 35 cP, more preferably in the range of 2 to 30 cP, and even more preferably in the range of 2 to 25 cP.

[0183] According to the present invention, the viscosity can be measured at room temperature using a vibratory viscometer VM-10A (SEKONIC).

[0184] It is believed that lower viscosity is important for preparing low-viscosity compositions suitable for inkjet printing. Therefore, (meth)acrylate monomers with viscosity values ​​within the aforementioned parameter range are particularly suitable for preparing compositions for inkjet printing. By using these (meth)acrylate monomers in the composition, the composition can still maintain a low viscosity suitable for inkjet printing even when mixed with another material, such as highly loaded semiconductor light-emitting nanoparticles.

[0185] In a preferred embodiment of the present invention, for large-area uniform inkjet printing, the boiling point (BP) of the (meth)acrylate monomer of chemical formula (I) is 250°C or higher, preferably in the range of 250°C to 350°C, even more preferably in the range of 280°C to 350°C, and even more preferably in the range of 300°C to 348°C.

[0186] It is believed that the high boiling point is also important for preparing compositions with low vapor pressure (preferably less than 0.001 mmHg) for large-area uniform printing. Preferably, (meth)acrylate monomers of formula (I) are used, with a viscosity of 25 cP or less at 25°C and a boiling point of at least 250°C or higher, preferably in the range of 250°C to 350°C, more preferably in the range of 300°C to 348°C, to prepare compositions suitable for large-area uniform inkjet printing, even when mixed with another material with a high loading, such as a high loading of semiconductor light-emitting nanoparticles.

[0187] According to the present invention, the BP can be estimated by known methods, such as those described in Science of Petroleum, Vol. II. p. 1281 (1398).

[0188] According to the present invention, any publicly available acrylate and / or methacrylate of any type represented by chemical formula (I) may preferably be used.

[0189] In particular, for the first aspect, any publicly available acrylate and / or methacrylate of any type represented by chemical formula (I) with a viscosity of 25 cP or less at 25°C can be used.

[0190] Furthermore, preferably, R in formula (I) 3 R of formula (I) 4 Each group is independently selected from the following groups, wherein the groups can be R a Replacement, preferably those not by R a replace.

[0191]

[0192]

[0193]

[0194] Particularly preferably, R in formula (I) 3 and R 4 Each time it appears, it is selected independently or differently from the following groups.

[0195]

[0196] Among them, in R 3 In this case, "*" indicates the connection point with the oxygen atom in the formula, or the connection point with the X atom in the formula. 2 The connection point, and in which, in R 4 In this case, "*" indicates the connection point with the oxygen atom in the formula, or the connection point with the X atom in the formula. 1 The connection point.

[0197] Furthermore, preferably, the formula (I) is NDDA (nonanediol diacrylate; BP: 342°C), HDDMA (hexanediol dimethacrylate; BP: 307°C), HDDA (hexanediol diacrylate; BP: 295°C), or DPGDA (BP: 314°C).

[0198] (DPGDA)

[0199] - Another reactive monomer

[0200] According to the present invention, in a preferred embodiment, the composition further comprises another reactive monomer, preferably having one or more functional groups, more preferably being a (meth)acrylate monomer different from the (meth)acrylate monomer of formula (I), preferably being a mono-(meth)acrylate monomer, more preferably being a mono-methacrylate monomer or a mono-acrylate monomer, and even more preferably being represented by the following formula (II).

[0201] (II)

[0202] X 3 It is an unsubstituted or substituted alkyl, aryl, or alkoxy group;

[0203] Preferably, the symbol X 3 yes

[0204] The "*" on the left side of the equation indicates the terminal base C=CR of equation (I). 5 The connection point;

[0205] l is 0 or 1;

[0206] R 5 It is a hydrogen atom, a halogen atom that is Cl, Br or F, a methyl, alkyl, aryl, alkoxy, ester or carboxylic acid group;

[0207] R 6 It is a straight-chain alkylene or alkeneoxy group having 1 to 25 carbon atoms, preferably R. 6 It is a straight-chain alkylene or alkeneoxy group having 1 to 15 carbon atoms, more preferably 1 to 5 carbon atoms.

[0208] It can be generated by one or more groups R a Substitution, wherein one or more non-adjacent CH2 groups can be replaced by R a C=CR a C≡C, Si(R) a )2、Ge(R a)2、Sn(R a 2. C=O, C=S, C=Se, C=NR a P(=O)(R) a SO, SO2, NR a OS or CONR a The substitution is possible, and one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2;

[0209] R 7 It is a straight-chain alkylene or alkeneoxy group having 1 to 25 carbon atoms, preferably R. 7 It is a straight-chain alkylene or alkeneoxy group having 1 to 15 carbon atoms, more preferably 1 to 5 carbon atoms.

[0210] It can be generated by one or more groups R a Substitution, wherein one or more non-adjacent CH2 groups can be replaced by R a C=CR a C≡C, Si(R) a )2、Ge(R a )2、Sn(R a 2. C=O, C=S, C=Se, C=NR a P(=O)(R) a SO, SO2, NR a OS or CONR a The substitution is possible, and one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2;

[0211] R a Each time it appears, it is the same or different of H, D, or an alkyl group having 1 to 20 carbon atoms, a cycloalkyl or alkoxy group having 3 to 40 carbon atoms, an aromatic ring system having 5 to 60 ring carbon atoms, or a heteroaromatic ring system having 5 to 60 carbon atoms, wherein the H atom can be replaced by D, F, Cl, Br, I; two or more adjacent substituents R a They can also form monocyclic or polycyclic, aliphatic, aromatic or heterocyclic ring systems with each other.

[0212] It is believed that (meth)acrylate monomers represented by the following chemical formula (II) exhibit viscosity values ​​that are much lower than those of (meth)acrylate monomers of formula (I). Therefore, by combining (meth)acrylate monomers represented by chemical formula (II) with those of chemical formula (I), compositions with much lower viscosity required for smooth inkjet printing can be achieved, preferably without reducing the external quantum efficiency (EQE) value.

[0213] It is believed that the combination can achieve low-viscosity compositions containing a large amount of another material, such as highly loaded semiconductor light-emitting nanoparticles. Therefore, it is particularly suitable for inkjet printing when the composition contains another material.

[0214] In a preferred embodiment of the present invention, for large-area uniform inkjet printing, the boiling point (BP) of the (meth)acrylate monomer of formula (II) is 250°C or higher, preferably 250°C or higher, more preferably in the range of 250°C to 350°C, even more preferably in the range of 280°C to 350°C, and even more preferably in the range of 300°C to 348°C.

[0215] In another preferred embodiment of the present invention, for large-area uniform inkjet printing, the boiling point (BP) of the (meth)acrylate monomer of formula (I) and / or the boiling point (BP) of the (meth)acrylate monomer of formula (II) is 250°C or higher, preferably the boiling points of both the (meth)acrylate monomers of formula (I) and formula (II) are 250°C or higher, more preferably in the range of 250°C to 350°C, even more preferably in the range of 280°C to 350°C, and even more preferably in the range of 300°C to 348°C.

[0216] Furthermore, preferably, R in formula (II) 7 Each time it appears, it is selected independently or differently from the following groups, wherein said groups can be R a Replacement, preferably those not by R a replace.

[0217]

[0218] When l is 1, "*" indicates a relationship with X. 3 R 6 The connection point, and when n is 0, it represents X in equation (II). 3 The connection point of the oxygen atom.

[0219] Furthermore, preferably, formula (II) is lauryl methacrylate (LM, viscosity 6 cP, BP: 142°C) or lauryl acrylate (LA, viscosity: 4.0 cP, BP: 313.2°C).

[0220] In a preferred embodiment of the invention, the composition contains a (meth)acrylate monomer of formula (II), wherein the mixing ratio of the (meth)acrylate monomer of formula (I) to the (meth)acrylate monomer of formula (II) is 1:99 to 99:1 (formula (I): formula (II)), preferably 5:95 to 50:50, more preferably 10:90 to 40:60, and even more preferably 15:85 to 25:75. Preferably, purified (meth)acrylate monomers represented by formulas (I) and (II) are used in the composition, and more preferably, both the (meth)acrylate monomer of formula (I) and the (meth)acrylate monomer of formula (II) are obtained or available by purification methods.

[0221] It is believed that a higher amount of (meth)acrylate monomers of Formula (II) relative to the total amount of (meth)acrylate monomers of Formula (I) results in an improved EQE of the composition, and from the perspective of the viscosity of the composition and the better inkjet performance of the composition, a mixing weight ratio of (meth)acrylate monomers of Formula (II) to the total amount of (meth)acrylate monomers of Formula (I) of less than 50% by weight is preferred.

[0222] Preferably, the reactive monomer, such as (meth)acrylate monomer, is purified by using a silica gel column or by molecular sieve purification before use.

[0223] It is believed that purification of impurities from (meth)acrylate monomers via silica gel column chromatography leads to improved QY of semiconductor luminescent nanoparticles in the composition.

[0224] In some embodiments of the present invention, the composition further comprises a (meth)acrylate monomer represented by the following chemical formula (III);

[0225] (III);

[0226] Where R 9 It is a hydrogen atom, a straight-chain alkyl group having 1 to 25 carbon atoms, or a (meth)acrylate group represented by chemical formula (IV).

[0227] (IV);

[0228] R 6 It is a hydrogen atom, a straight-chain alkyl group having 1 to 25 carbon atoms, or a (meth)acrylate group represented by chemical formula (V).

[0229] (V);

[0230] R 7It is a hydrogen atom, a straight-chain alkyl group having 1 to 25 carbon atoms, or a (meth)acrylate group represented by chemical formula (VI).

[0231] (VI);

[0232] Where R 8a R 8b and R 8c Each time it appears, it is either H or CH3, either independently or dependently.

[0233] Where R 9 R 10 and R 11 At least one of them is a (meth)acrylate group, preferably R 9 R 10 and R 11 Two of them are (meth)acrylate groups, and the other is a hydrogen atom or a straight-chain alkyl group having 1 to 25 carbon atoms. Preferably, the (meth)acrylate monomer of formula (III) has an electrical conductivity (S / cm) of 1.0. * 10 -10 Or lower, preferably 5.0 * 10 -11 Or lower, more preferably at 5.0 * 10 -11 Up to 1.0 * 10 -15 Within the range, more preferably within 5.0. * 10 -12 Up to 1.0 * 10 -15 Within the range.

[0234] It is believed that (meth)acrylate monomers of formula (III) can be used to improve the robustness of layers made from the composition after inkjet printing.

[0235] According to the present invention, a known (meth)acrylate monomer represented by the following chemical formula (III) can be used to improve the robustness of inkjet-printed and crosslinked layers.

[0236] Very preferably, trimethylolpropane triacrylate (TMPTA) is used as the (meth)acrylate monomer of formula (III).

[0237] In a preferred embodiment of the invention, based on the total amount of (meth)acrylate monomers in the composition, the amount of (meth)acrylate monomers of formula (III) is in the range of 0.001 wt% to 25 wt%, more preferably in the range of 0.1 wt% to 15 wt%, even more preferably in the range of 1 wt% to 10 wt%, and even more preferably in the range of 3 wt% to 7 wt%.

[0238] Preferably, the reactive monomer, such as (meth)acrylate monomer, is purified by using a silica gel column or by molecular sieve purification before use.

[0239] It is believed that purification of impurities from (meth)acrylate monomers via silica gel column chromatography leads to improved QY of semiconductor luminescent nanoparticles in the composition.

[0240] According to the present invention, in a preferred embodiment, the viscosity of the composition is 35 cP or lower at room temperature, preferably in the range of 1 to 35 cP, more preferably in the range of 2 to 30 cP, and even more preferably in the range of 2 to 25 cP.

[0241] In a preferred embodiment of the invention, based on the total composition, the composition contains 10% by weight or less of a solvent, more preferably 5% by weight or less, and more preferably a solvent-free composition. Preferably, the composition does not contain any solvent selected from one or more of the following groups: ethylene glycol monoalkyl ethers, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; propylene glycol monoalkyl ethers, such as propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, and propylene glycol monopropyl ether; ethylene glycol alkyl ether acetates, such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol alkyl ether acetates, such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, and propylene glycol monomethyl ether acetate. Diol monopropyl ether acetate; ketones, such as methyl ethyl ketone, acetone, methyl pentyl ketone, methyl isobutyl ketone and cyclohexanone; alcohols, such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, triethylene glycol and glycerol; esters, such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and ethyl lactate; and cyclic esters, such as γ-butyrolactone; chlorinated hydrocarbons, such as chloroform, dichloromethane, chlorobenzene, trimethylbenzene, such as 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3-trimethylbenzene, dodecylbenzene, cyclohexylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 3-isopropylbiphenyl, 3-methylbiphenyl, 4-methylbiphenyl and dichlorobenzene, preferably the solvent being propylene glycol alkyl ether acetate, alkyl acetate, ethylene glycol monoalkyl ether, propylene glycol and propylene glycol monoalkyl ether.

[0242] It is believed that less than 10% by weight of solvent in the composition results in improved inkjet printing, and it can avoid a second or more inkjet printing on the same pixel after the solvent evaporates.

[0243] -Light-emitting part (110)

[0244] In a preferred embodiment of the present invention, the light-emitting portion is an organic light-emitting material and / or an inorganic light-emitting material. Preferably, the organic light-emitting material is an organic dye or an organic light-emitting material used in organic light-emitting diode devices. Preferably, the inorganic light-emitting material is an inorganic phosphor and / or a semiconductor light-emitting nanoparticle, such as a quantum (size) material.

[0245] In some embodiments of the present invention, the total amount of the light-emitting portion (110) is in the range of 0.1% to 90% by weight, preferably 10% to 70% by weight, and more preferably 30% to 50% by weight, based on the total amount of the first pixel (161).

[0246] -iii) Semiconductor light-emitting nanoparticles

[0247] According to the present invention, the term "semiconductor" refers to a material having an electrical conductivity at room temperature between that of a conductor (e.g., copper) and an insulator (e.g., glass). Preferably, a semiconductor is a material whose electrical conductivity increases with temperature.

[0248] The term "nanosize" refers to a size between 0.1 nm and 150 nm, more preferably between 3 nm and 50 nm.

[0249] Therefore, according to the present invention, "semiconductor light-emitting nanoparticles" refer to light-emitting materials with a size between 0.1 nm and 150 nm, more preferably between 3 nm and 50 nm, and having an electrical conductivity between that of a conductor (e.g., copper) and an insulator (e.g., glass) at room temperature. Preferably, the semiconductor is a material whose electrical conductivity increases with temperature, and has a size between 0.1 nm and 150 nm, more preferably between 0.5 nm and 150 nm, more preferably between 1 nm and 50 nm.

[0250] According to the present invention, the term "size" refers to the average diameter of the longest axis of semiconductor nanoscale light-emitting particles.

[0251] The average diameter of the semiconductor nanoscale luminescent nanoparticles was calculated based on 100 semiconductor luminescent nanoparticles in TEM images created by a Tecnai G 2 Spirit Twin T-12 transmission electron microscope.

[0252] In a preferred embodiment of the present invention, the semiconductor light-emitting nanoparticles of the present invention are quantum-sized materials.

[0253] According to the present invention, the term "quantum size" refers to the size of a semiconductor material itself without ligands or other surface modifications, which can exhibit quantum confinement effects, as described, for example, in ISBN: 978-3-662-44822-9.

[0254] For example, CdS, CdSe, CdTe, ZnS, ZnSe, ZnSeS, ZnTe, ZnO, GaAs, GaP, GaSb, HgS, HgSe, HgSe, HgTe, InAs, InP, InPZn, InPZnS, InPZnSe, InPZnSeS, InPZnGa, InPGaS, InPGaSe, InPGaSeS, InPZnGaSeS, and InPGa, InCdP, InPCdS, InPCdSe, InSb, AlAs, AlP, AlSb, Cu2S, Cu2Se, CuInS2, CuInSe2, Cu2(ZnSn)S4, Cu2(InGa)S4, TiO2 alloys, and any combination thereof can be used.

[0255] In a preferred embodiment of the present invention, the first semiconductor material includes at least one element from Group 13 of the periodic table and one element from Group 15 of the periodic table. Preferably, the element from Group 13 is In and the element from Group 15 is P. More preferably, the first semiconductor material is selected from InP, InPZn, InPZnS, InPZnSe, InPZnSeS, InPZnGa, InPGaS, InPGaSe, InPGaSeS, InPZnGaSeS, and InPGa.

[0256] According to the present invention, there are no particular limitations on the shape type of the core of the semiconductor light-emitting nanoparticle to be synthesized and the shape of the semiconductor light-emitting nanoparticle.

[0257] For example, spherical, elongated, star-shaped, polyhedral, pyramidal, tetrapod-shaped, tetrahedral, platelet-shaped, conical, and irregularly shaped nuclear and / or semiconductor luminescent nanoparticles can be synthesized.

[0258] In some embodiments of the present invention, the average diameter of the nucleus is in the range of 1.5 nm to 3.5 nm.

[0259] The average diameter of the nucleus was calculated based on 100 semiconductor luminescent nanoparticles in a TEM image created by a Tecnai G2 Spirit Twin T-12 transmission electron microscope.

[0260] In some embodiments of the present invention, at least one shell comprises or is composed of a first element of group 12 of the periodic table and a second element of group 16 of the periodic table, preferably, the first element is Zn and the second element is S, Se or Te; preferably, the first shell directly covering the core comprises or is composed of a first element of group 12 of the periodic table and a second element of group 16 of the periodic table, preferably, the first element is Zn and the second element is S, Se or Te.

[0261] In a preferred embodiment of the present invention, at least one shell (first shell) is represented by the following formula (XI), and preferably, the shell that directly covers the core is represented by the chemical formula (XI);

[0262] ZnS x Se y Te z - (XI)

[0263] Where 0≤x≤1, 0≤y≤1, 0≤z≤1, and x+y+z=1, preferably 0≤x≤1, 0≤y≤1, z=0, and x+y=1, preferably the shell is ZnSe or ZnS. x Se y ZnSe y Te z or ZnS x Te z .

[0264] In some embodiments of the present invention, the shell is an alloy shell or a gradient shell, preferably the gradient shell is ZnS. x Se y ZnSe y Te z or ZnS x Te z ZnS is preferred. x Se y .

[0265] In some embodiments of the present invention, the semiconductor light-emitting nanoparticles further include a second shell located on the said shell, preferably the second shell includes or is composed of a third element of Group 12 of the periodic table and a fourth element of Group 16 of the periodic table, more preferably the third element is Zn and the fourth element is S, Se or Te, provided that the fourth element and the second element are not the same.

[0266] In a preferred embodiment of the present invention, the second shell is represented by the following formula (XI'),

[0267] ZnS x Se y Te z - (XI´)

[0268] Where 0≤x≤1, 0≤y≤1, 0≤z≤1, and x+y+z=1, preferably, the shell is ZnSe or ZnS. x Se y ZnSe y Te z or ZnS x Te z The condition is that the first and second shells are not the same.

[0269] In some embodiments of the present invention, the second shell may be an alloy shell.

[0270] In some embodiments of the present invention, the semiconductor light-emitting nanoparticles may further include one or more additional shells on the second shell, as a multi-shell structure.

[0271] According to the present invention, the term "multi-shell" refers to a stacked shell consisting of three or more shell layers.

[0272] For example, CdSe / CdS, CdSeS / CdZnS, CdSeS / CdS / ZnS, ZnSe / CdS, CdSe / ZnS, InP / ZnS, InP / ZnSe, InP / ZnSe / ZnS, InZnP / ZnS, InZnP / ZnSe, InZnP / ZnSe / ZnS, InGaP / ZnS, InGaP / ZnSe, InGaP / ZnSe / ZnS, InZnPS / ZnS, InZnPS ZnSe, InZnPS / ZnSe / ZnS, ZnSe / CdS, ZnSe / ZnS or any combination of these. Preference is given to InP / ZnS, InP / ZnSe, InP / ZnSe / ZnS, InZnP / ZnS, InZnP / ZnSe, InZnP / ZnSe / ZnS, InGaP / ZnS, InGaP / ZnSe, InGaP / ZnSe / ZnS.

[0273] Such semiconductor luminescent nanoparticles are publicly available (e.g., from Sigma Aldrich) and / or can be synthesized using methods described, for example, in US 7,588,828 B, US 8,679,543 B, and Chem. Mater. 2015, 27, pp 4893-4898.

[0274] In some embodiments of the present invention, the composition comprises two or more semiconductor light-emitting nanoparticles.

[0275] In some embodiments of the present invention, the composition comprises a variety of semiconductor light-emitting nanoparticles.

[0276] In some embodiments of the present invention, the total amount of semiconductor light-emitting nanoparticles is in the range of 0.1% to 90% by weight, preferably 10% to 70% by weight, and more preferably 30% to 50% by weight, based on the total amount of the composition.

[0277] -ligands

[0278] In some embodiments of the present invention, optionally, the semiconductor light-emitting nanoparticles may be directly coated with one or more ligands, or the outermost surface of the inorganic portion of the semiconductor light-emitting nanoparticles may be directly coated with another ligand, and the other ligand may be further coated with a polymer.

[0279] As other ligands, phosphine and phosphine oxides such as trioctylphosphine oxide (TOPO), trioctylphosphine (TOP), and tributylphosphine (TBP) can be used; phosphonic acids such as dodecylphosphine acid (DDPA), tridecylphosphine acid (TDPA), octadecylphosphine acid (ODPA), and hexylphosphine acid (HPA); amines such as oleylamine, dodecylamine (DDA), tetradecylamine (TDA), hexadecylamine (HDA), and octadecylamine (ODA), oleylamine (OLA), 1-octadecene (ODE); thiols such as hexadecylthiol and hexanethiol; mercaptocarboxylic acids such as mercaptopropionic acid and mercaptoundecanoic acid; carboxylic acids such as oleic acid, stearic acid, and myristic acid; acetic acid, polyethylene imine (PEI), monofunctional PEG thiols (mPEG-thiols), or derivatives of mPEG thiols, and any combination thereof.

[0280] Examples of such ligands have been described, for example, in published international patent application WO 2012 / 059931 A.

[0281] -scattering particles

[0282] According to the present invention, small particles of known inorganic oxides, such as SiO2, SnO2, CuO, CoO, Al2O3, TiO2, Fe2O3, Y2O3, ZnO, ZnS, and MgO, can be used as scattering particles; organic particles, such as polymerized polystyrene and polymerized PMMA; inorganic hollow oxides, such as hollow silica, or any combination thereof. Based on the total solid content of the layer, the amount of scattering particles is preferably 4% by weight or less, preferably in the range of 4% to 0% by weight, more preferably in the range of 1% to 0% by weight, and even more preferably the layer and / or composition contains no scattering particles.

[0283] In some embodiments of the invention, the composition comprises

[0284] iii) At least one semiconductor light-emitting nanoparticle, comprising a first semiconductor nanoparticle, optionally covering at least a portion of the first semiconductor nanoparticle with one or more shells, preferably having an EQE value of 23% or higher, more preferably 24% or higher and less than 95%.

[0285] According to the present invention, as a transparent polymer, various known transparent polymers suitable for optical devices, such as those described in WO 2016 / 134820A, can be preferably used.

[0286] According to the present invention, the term "transparent" means that at least about 60% of the incident light is transmitted at the thickness used in the optical medium and at the wavelength or wavelength range used during the operation of the optical medium. Preferably, it is 70% or greater, more preferably 75% or greater, and most preferably 80% or greater.

[0287] According to the present invention, the term "polymer" refers to a material having repeating units and a weight-average molecular weight (Mw) of 1000 g / mol or higher.

[0288] Molecular weight M w Determination relative to internal polystyrene standards was achieved using GPC (gel permeation chromatography).

[0289] In some embodiments of the present invention, the glass transition temperature (Tg) of the transparent polymer is 70°C or higher and 250°C or lower.

[0290] Tg is measured based on the change in heat capacity observed in differential scanning colorimetry, as described, for example, in http: / / pslc.ws / macrog / dsc.htm; Rickey J Seyler, Assignment of the Glass Transition, ASTM publication code number (PCN) 04-012490-50.

[0291] For example, transparent polymers used as transparent matrix materials include poly(meth)acrylates, epoxy resins, polyurethanes, and polysiloxanes.

[0292] In a preferred embodiment of the invention, the weight-average molecular weight (Mw) of the polymer used as the transparent matrix material is in the range of 1,000 to 300,000 g / mol, more preferably 10,000 to 250,000 g / mol.

[0293] According to the present invention, known antioxidants, free radical quenchers, photoinitiators and / or surfactants, such as those described in WO 2016 / 134820A, may preferably be used.

[0294] According to the present invention, preferably, the composition further comprises one or more of the following materials:

[0295] A) Another light-emitting portion, which is different from the aforementioned light-emitting portion, preferably the light-emitting portion is an organic light-emitting material and / or an inorganic light-emitting material, more preferably the organic light-emitting material is an organic dye, or an organic light-emitting material used in organic light-emitting diode devices, more preferably the inorganic light-emitting material is an inorganic phosphor and / or a quantum material, preferably the light-emitting portion includes a ligand, more preferably the light-emitting portion includes an alkyl or alkenyl ligand having 2 to 25 carbon atoms;

[0296] B) Another (meth)acrylate monomer; and

[0297] C) Optically transparent polymers, antioxidants, free radical quenchers, photoinitiators and / or surfactants.

[0298] In some embodiments of the present invention, preferably, the composition of the present invention comprises

[0299] v) Scattering particles; and

[0300] vii) at least one polymer configured such that the polymer can disperse scattering particles in the composition;

[0301] The polymer comprises at least a phosphine group, a phosphine oxide group, a phosphate ester group, a phosphonate ester group, a thiol group, a tertiary amine group, a carboxyl group, a heterocyclic group, a silyl group, a sulfonic acid group, a hydroxyl group, a phosphonic acid group, or a combination thereof, preferably the polymer comprises a tertiary amine group, a phosphine oxide group, a phosphonic acid group, or a phosphate ester group.

[0302] According to the present invention, a polymer configured such that the polymer can disperse scattering particles in a composition comprises at least one repeating unit A, said repeating unit A comprising phosphine, phosphine oxide, phosphate ester, phosphonate, thiol, tertiary amine, carboxyl, heterocyclic, silyl, sulfonic acid, hydroxyl, phosphonic acid or a combination thereof, preferably repeating unit A comprising tertiary amine, phosphine oxide, phosphonic acid or phosphate ester.

[0303] In some embodiments of the present invention, repeating unit A and repeating unit B constitute repeating units.

[0304] Even more preferably, repeating unit A comprises a tertiary amine represented by the following chemical formula (VII),

[0305] NR 12 R 13 R 14 - - (VII)

[0306] Where R 12 It is a hydrogen atom, a straight-chain or branched alkyl group having 1 to 30 carbon atoms, or an aryl group having 1 to 30 carbon atoms; R 13 It is a hydrogen atom, a straight-chain or branched alkyl group having 1 to 30 carbon atoms, or an aryl group having 1 to 30 carbon atoms; R12 and R 13 They can be the same or different from each other; R 14 It is a single bond, a straight-chain or branched alkylene group having 1 to 30 carbon atoms, an alkenyl group having 1 to 30 carbon atoms, or a (poly)oxaalkylene group having 1 to 30 carbon atoms.

[0307] More preferably, R 12 It is a straight-chain or branched alkyl group having 1 to 30 carbon atoms; R 13 It is a straight-chain or branched alkyl group having 1 to 30 carbon atoms; R 12 and R 13 They can be the same as or different from each other.

[0308] In addition, R is preferred 12 It is methyl, ethyl, n-propyl, or n-butyl; R 13 It is methyl, ethyl, n-propyl, or n-butyl.

[0309] According to the present invention, in a preferred embodiment, repeating unit A is salt-free.

[0310] In a preferred embodiment of the invention, the polymer is a copolymer selected from graft copolymers, block copolymers, alternating copolymers, and random copolymers. Preferably, the copolymer comprises repeating unit A and repeating unit B which does not contain any phosphine groups, phosphine oxide groups, phosphate ester groups, phosphonate ester groups, thiol groups, tertiary amine groups, carboxyl groups, heterocyclic groups, silyl groups, sulfonic acids, hydroxyl groups, phosphonic acids, or combinations thereof. More preferably, the copolymer is a block copolymer represented by the following chemical formula (VIII) or (IX).

[0311] A n – B m - (VIII)

[0312] B o – A n – B m - (IX)

[0313] Wherein the symbol “A” represents repeating unit A; the symbol “B” represents repeating unit B; the symbols “n”, “m” and “o” are integers from 1 to 100, preferably from 5 to 75, more preferably from 7 to 50, each time they appear independently or dependently; even more preferably, repeating unit B comprises a polymer chain selected from (poly)ethylene, (poly)phenylene, polydivinylbenzene, (poly)ether, (poly)ester, (poly)amide, (poly)urethane, (poly)carbonate, polylactic acid, (poly)vinyl ester, (poly)vinyl ether, polyvinyl alcohol, polyvinylpyrrolidone, cellulose and any derivatives thereof.

[0314] In a preferred embodiment of the invention, the polymer chain of repeating unit B is polyethylene glycol.

[0315] More preferably, the repeating unit B comprises a chemical structure represented by the following chemical formula (X),

[0316] Chemical formula (X)

[0317] Where the chemical formula (X), R 15 It is a hydrogen atom or a methyl group; R 16 is an alkyl group having 1 to 10 carbon atoms; and n is an integer from 1 to 5, where "*" indicates a connection point with another polymer repeating unit or the end of a polymer.

[0318] More preferably, R 15 It can be a hydrogen atom or a methyl group, R 16 It can be an ethyl group, and n is an integer from 1 to 5.

[0319] In some embodiments of the present invention, the surface of the core of the semiconductor light-emitting nanoparticle or the outermost surface of one or more shells may be partially or completely coated with a polymer.

[0320] By using ligand exchange methods, such as those described in Thomas Nann, Chem. Commun., 2005, 1735–1736, DOI: 10.1039 / b-414807j, polymers can be introduced onto the surface of the core or the outermost surface of the core of semiconductor luminescent nanoparticles.

[0321] According to the present invention, in some embodiments, the content of the polymer is in the range of 1 wt% to 500 wt% relative to the total weight of the semiconductor light-emitting nanoparticles, more preferably in the range of 20 wt% to 350 wt%, and even more preferably in the range of 50 wt% to 200 wt%.

[0322] In a preferred embodiment of the invention, the weight-average molecular weight (Mw) of the polymer is in the range of 200 g / mol to 30,000 g / mol, preferably 250 g / mol to 2,000 g / mol, and more preferably 400 g / mol to 1,000 g / mol.

[0323] The molecular weight Mw was determined relative to an internal polystyrene standard using GPC (gel permeation chromatography).

[0324] As a polymer, commercially available wetting and dispersing additives that are soluble in nonpolar and / or low-polarity organic solvents are preferred. Examples include BYK-111, BYK-LPN6919, BYK-103, BYK-P104, BYK-163 ([trademark], from BYKcom.), TERPLUS MD1000 series, such as MD1000, MD1100 ([trademark], from Otsuka Chemical), poly(ethylene glycol) methyl etheramine (Sigma-Ald 767565 [trademark], from Sigma Aldrich), polyester bis-MPA dendritic unit, 32 hydroxyl, 1 thiol (Sigma-Ald 767115 [trademark], from Sigma Aldrich), LIPONOL DA-T / 25 (from Lion Specialty Chemicals Co.), carboxymethyl cellulose (from Polyscience, etc.), in, for example, "Marc Thiry et al., ACSNANO, American Chemical Society, Vol. 5, No. 6, pp 4965 –4973, 2011". Another wetting and dispersing additive disclosed in “Kimihiro Susumu, et. al., J. Am. Chem. Soc. 2011, 133, pp 9480-9496”.

[0325] Therefore, in some embodiments of the present invention, the composition comprises at least a (meth)acrylate monomer of formula (I), a (meth)acrylate monomer of formula (II), and a polymer configured such that the polymer can disperse the scattering particles in the composition, wherein the mixing ratio of the (meth)acrylate monomer of formula (I): the (meth)acrylate monomer of formula (II): the polymer is from 10:89:1 to 50:40:10, preferably in the range of 15:82:3 to 30:60:10.

[0326] In some embodiments of the invention, the composition comprises, substantially comprises, or is derived from, at least one polymer derived from or potentially derived from the (meth)acrylate monomer of the composition of the invention.

[0327] In a preferred embodiment of the invention, the polymer is derived from or may be derived from all (meth)acrylate monomers in the composition, for example, at least (meth)acrylate monomers of formula (I) and / or (meth)acrylate monomers of formula (II).

[0328] -QY calculation

[0329] The quantum yield (QY) of the composition was measured using an absolute PL quantum yield spectrometer C9920-02 (Hamamatsu Photonics KK) and the following formula was used.

[0330] Quantum yield (QY) = number of photons emitted by the sample / number of photons absorbed by the sample.

[0331] To improve the output coupling efficiency from optical media containing semiconductor light-emitting nanoparticles (e.g., optical films containing quantum-sized materials), several methods have been proposed, such as doping the film and / or adjacent films with scattering particles, reducing the refractive index of the film by doping with hollow silica particles, and placing suitable shaped structures (see Proceedings of SPIE, pp. 184, 5519-33, 2004). Among these, placing structured films on films containing quantum materials is best suited for large-scale TV applications using local dimming techniques to achieve high dynamic range. Scattering particles are detrimental to dimming techniques because scattered light causes color blurring, and due to the limited volume of hollow silica particles, it is difficult to reduce the refractive index of the film sufficiently to achieve practical levels. Combinations of refractive index reduction and the placement of structured films can also be applied.

[0332] In another aspect, the present invention further relates to cured compositions obtained or available by the method of the present invention.

[0333] In another aspect, the present invention further relates to layers obtained or available by the method of the present invention.

[0334] On another aspect, the present invention also relates to a layer comprising a light-emitting portion, a matrix material, and scattering particles, wherein, based on the total amount of the layer, the total amount of the light-emitting portion ranges from 0.1% by weight to 90% by weight, more preferably from 10% by weight to 70% by weight, and even more preferably from 30% by weight to 50% by weight; and

[0335] The total amount of scattering particles, based on the total amount of the layer, is 10% by weight or less, preferably 5% to 1% by weight, more preferably 4% to 2% by weight. Preferably, the layer is configured to achieve an EQE value of 20% or higher, more preferably the EQE value is in the range of 20% to 99%, more preferably the EQE value is in the range of 30% to 50%, and even more preferably the EQE value is in the range of 30% to 40%. For blue-green conversion efficiency, the layer is preferably a patterned layer.

[0336] In a preferred embodiment of the present invention, the thickness of the layer is in the range of 1 to 50 μm, preferably 5 to 15 μm, more preferably 8 to 15 μm, and even more preferably 8 to 12 μm.

[0337] On the other hand, the present invention also relates to a color conversion device (100) comprising at least a first pixel (161) which is partially or completely filled with the aforementioned cured composition or filled with the layer of the present invention, and a dam (150) comprising at least a polymer material, preferably, the color conversion device (100) further comprising a support medium (170).

[0338] - First pixel (161)

[0339] According to the present invention, the first pixel (161) comprises at least a matrix material (120) containing a light-emitting portion (110). In a preferred embodiment, the first pixel (161) is a solid layer obtained or available by curing a composition of the present invention comprising at least one acrylate monomer and at least one light-emitting portion (110), preferably, the curing is photocuring, thermal curing or a combination of photocuring and thermal curing by light irradiation.

[0340] In a preferred embodiment, the height of the embankment (150) is in the range of 0.1 to 100 μm, preferably 1 to 50 μm, more preferably 1 to 25 μm, and even more preferably 5 to 20 μm.

[0341] In some embodiments of the present invention, the layer thickness of the pixel (161) is in the range of 0.1 to 100 μm, preferably 1 to 50 μm, and more preferably 5 to 25 μm.

[0342] In some embodiments of the present invention, the color conversion device (100) further includes a second pixel (162). Preferably, the device (100) includes at least the first pixel (161), the second pixel (162), and the third pixel (163). More preferably, the first pixel (161) is a red pixel, the second pixel (162) is a green pixel, and the third pixel (163) is a blue pixel. Even more preferably, the first pixel (161) contains a red light-emitting portion (110R), the second color pixel (162) contains a green light-emitting portion (110G), and the third pixel (163) does not contain any light-emitting portion.

[0343] In some embodiments, at least one pixel (160) further includes at least one light scattering particle (130) in the matrix material (120), preferably, the pixel (160) includes multiple light scattering particles (130).

[0344] In some embodiments of the invention, the first pixel (161) consists of one pixel or two or more sub-pixels, the sub-pixels being configured to emit red when illuminated by excitation light, and more preferably, the sub-pixels contain the same light-emitting portion (110).

[0345] In a preferred embodiment, the dam (150) is configured to determine the area of ​​the first pixel (161), and at least a portion of the dam (150) directly contacts at least a portion of the first pixel (161). Preferably, the second polymer of the dam (150) directly contacts at least a portion of the first polymer of the first pixel (161).

[0346] In a preferred embodiment, the dam (150) is photolithographically patterned, and the first pixel (161) is surrounded by the dam (150). Preferably, the first pixel (161), the second pixel (162), and the third pixel (163) are all surrounded by the photolithographically patterned dam (150).

[0347] According to the present invention, the well-known dike composition and well-known dike manufacturing method described, for example, in WO 2021 / 018927A1 can be used.

[0348] -Matrix material (120)

[0349] In a preferred embodiment, the matrix material (120) comprises a (meth)acrylate polymer, preferably a methacrylate polymer, an acrylate polymer or a combination thereof, more preferably an acrylate polymer, and even more preferably the matrix material (120) is obtained or available from a composition of the present invention containing at least one acrylate monomer, further more preferably the matrix material (120) is obtained or available from a composition of the present invention containing at least one diacrylate monomer, particularly preferably the matrix material (120) is obtained or available from a composition of the present invention containing at least one diacrylate monomer and one monoacrylate monomer, preferably the composition is a photosensitive composition.

[0350] - Support medium (170)

[0351] In some embodiments of the present invention, the support medium (170) is a substrate, more preferably a transparent substrate.

[0352] Typically, the substrate, such as a transparent substrate, can be flexible, semi-rigid, or rigid.

[0353] Known transparent substrates suitable for optical devices can be used as needed.

[0354] Preferably, as the transparent substrate, a transparent polymer substrate, a glass substrate, a thin glass substrate stacked on a transparent polymer film, a transparent metal oxide (e.g., silicone oxide, aluminum oxide, titanium oxide), or a polymer film substrate having a transparent metal oxide can be used. Even more preferably, it is a transparent polymer substrate or a glass substrate.

[0355] The transparent polymer substrate may be made of polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyetheretherketone, polysulfone, polyethersulfone, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene copolymer, tetrafluoroethylene hexafluoropolymer copolymer, or any combination thereof.

[0356] The term "transparency" refers to a transmittance of at least about 60% of incident light at the thickness used in a photovoltaic device and at the wavelength or wavelength range used during photovoltaic cell operation. Preferably, it is 70% or greater, more preferably 75% or greater, and most preferably 80% or greater.

[0357] -use

[0358] In another aspect, the present invention relates to the use of the color conversion device (100) of the present invention in an optical device (300), the optical device (300) comprising at least one functional medium (320, 420, 520) configured to modulate light or configured to emit light.

[0359] -Optical devices

[0360] In another aspect, the present invention further relates to optical devices (300, 400, 500) comprising at least one color conversion device (100) and a functional medium (320, 420, 520) configured to modulate light or to emit light.

[0361] In some embodiments of the present invention, the optical device may be a liquid crystal display (LCD), an organic light-emitting diode (OLED), a backlight unit for an optical display, a light-emitting diode (LED), a microelectromechanical system (hereinafter referred to as "MEMS"), an electrowetting display or an electrophoretic display, an illumination device and / or a solar cell.

[0362] Figures 4 to 6 Some embodiments of the optical device of the present invention are shown.

[0363] Preferred implementation scheme

[0364] 1. A method for preparing a cured composition, comprising at least the following steps:

[0365] a) Using light to irradiate the composition as the first light irradiation;

[0366] b) Irradiating the composition with light as a second light irradiation;

[0367] The composition comprises at least one luminescent portion and a reactive monomer, preferably the monomer having one or more functional groups, more preferably (meth)acrylate monomer;

[0368] The intensity of the light irradiated by the first light and the intensity of the light irradiated by the second light satisfy the following formula (I).

[0369] The intensity of the light illuminating the first ray is less than the intensity of the light illuminating the second ray. (I)

[0370] 2. The method of embodiment 1, wherein the peak wavelength of the light irradiated by the first light and the peak wavelength of the light irradiated by the second light are independently within the range of 200 to 450 nm, preferably 365 to 410 nm, and more preferably 375 to 405 nm.

[0371] 3. The method according to implementation scheme 1 or 2, wherein the irradiation time of the first light irradiation in step a) is in the range of 1 second to 500 seconds, and the irradiation time of the second light irradiation in step b) is in the range of 1 second to 500 seconds; preferably, the irradiation time of the first light irradiation in step a) is in the range of 2 seconds to 100 seconds, and the irradiation time of the second light irradiation in step b) is in the range of 2 seconds to 100 seconds; more preferably, the irradiation time of the first light irradiation in step a) is in the range of 3 seconds to 50 seconds, and the irradiation time of the second light irradiation in step b) is in the range of 5 seconds to 50 seconds; even more preferably, the irradiation time of the first light irradiation in step a) is in the range of 4 seconds to 20 seconds, and the irradiation time of the second light irradiation in step b) is in the range of 7 seconds to 20 seconds.

[0372] 4. The method of any one of implementations 1 to 3, wherein the intensity of the light irradiated by the first light in step (a) is 0.1 mW / cm². 2 Up to 20 mW / cm 2 Within the range, the intensity of the light irradiated by the second light in step (b) is 20 mW / cm². 2 Up to 100 W / cm 2 Within the specified range, preferably, the intensity of the light irradiated by the first light in step (a) is within 0.5 mW / cm². 2 Up to 10 mW / cm 2 Within the range, the intensity of the light irradiated by the second light in step (b) is 100 mW / cm². 2 Up to 10 W / cm 2 More preferably, the intensity of the light irradiated by the first light in step (a) is within the range of 1 mW / cm². 2 Up to 5 mW / cm 2 Within the range, the intensity of the light irradiated by the second light in step (b) is 200 mW / cm². 2 Up to 5 W / cm2 Within the range.

[0373] 5. The method of any one of embodiments 1 to 4, wherein the composition comprises a plurality of light-emitting portions, and based on the total amount of the composition, preferably the total amount of light-emitting portions is in the range of 0.1 wt% to 90 wt%, more preferably 10 wt% to 70 wt%, and even more preferably 30 wt% to 50 wt%.

[0374] 6. The method of any one of embodiments 1 to 5, wherein the composition comprises scattering particles, wherein the total amount of scattering particles is 10% by weight or less, preferably 10% to 0% by weight, more preferably in the range of 5% to 1% by weight, and even more preferably in the range of 4% to 2% by weight, based on the total solid content of the composition.

[0375] 7. The method according to any one of embodiments 1 to 6, wherein the reactive monomer is a (meth)acrylate monomer selected from mono(meth)acrylate monomers, di(meth)acrylate monomers, or tri(meth)acrylate monomers; more preferably, it is a di-methacrylate monomer or a di-acrylate monomer, a tri-methacrylate monomer, or a tri-acrylate monomer; even more preferably, it is represented by the following chemical formula (I).

[0376] (I)

[0377] in,

[0378] X 1 It is an unsubstituted or substituted alkyl, aryl, alkoxy, or ester group;

[0379] X 2 It is an unsubstituted or substituted alkyl, aryl, alkoxy, or ester group;

[0380] R 1 It is a hydrogen atom, a halogen atom that is Cl, Br or F, a methyl, alkyl, aryl, alkoxy, ester or carboxylic acid group;

[0381] R 2 It is a hydrogen atom, a halogen atom that is Cl, Br or F, a methyl, alkyl, aryl, alkoxy, ester or carboxylic acid group;

[0382] Preferably, the symbol X 1 yes ,

[0383] In this equation, the "*" on the left side indicates the terminal base C=CR of equation (I). 1 The carbon atom connection point, the "*" on the right indicates the symbol X in formula (I). 2 The connection point;

[0384] n is 0 or 1;

[0385] Preferably, the symbol X 2 yes ,

[0386] In this context, the asterisk (*) on the left-hand side of the equation represents the symbol X in equation (I). 1 The connection point, the "*" on the right indicates the connection with the end base C=CR of equation (I). 2 The connection point;

[0387] m is 0 or 1;

[0388] Preferably, at least m or n is 1;

[0389] R 3 It is a straight-chain alkylene or alkoxide having 1 to 25 carbon atoms, a cycloalkyl having 3 to 25 carbon atoms, or an aryl having 3 to 25 carbon atoms, preferably R. 3 It is a straight-chain alkylene or alkeneoxy group having 1 to 15 carbon atoms, more preferably 1 to 5 carbon atoms.

[0390] It can be generated by one or more groups R a Substitution, wherein one or more non-adjacent CH2 groups can be replaced by R a C=CR a C≡C, Si(R) a )2、Ge(R a )2、Sn(R a 2. C=O, C=S, C=Se, C=NR a P(=O)(R) a SO, SO2, NR a OS or CONR a The substitution is possible, and one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2;

[0391] R 4 It is a straight-chain alkylene or alkoxide having 1 to 25 carbon atoms, a cycloalkyl having 3 to 25 carbon atoms, or an aryl having 3 to 25 carbon atoms, preferably R. 4 It is a straight-chain alkylene or alkeneoxy group having 1 to 15 carbon atoms, more preferably 1 to 5 carbon atoms.

[0392] It can be generated by one or more groups R a Substitution, wherein one or more non-adjacent CH2 groups can be replaced by R a C=CR a C≡C, Si(R) a )2、Ge(R a )2、Sn(R a 2. C=O, C=S, C=Se, C=NRa P(=O)(R) a SO, SO2, NR a OS or CONR a The substitution is possible, and one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2;

[0393] R a Each time it appears, it is the same or different of H, D, or an alkyl group having 1 to 20 carbon atoms, a cycloalkyl or alkoxy group having 3 to 40 carbon atoms, an aromatic ring system having 5 to 60 ring carbon atoms, or a heteroaromatic ring system having 5 to 60 carbon atoms, wherein the H atom can be replaced by D, F, Cl, Br, I; two or more adjacent substituents R a They can also form monocyclic or polycyclic, aliphatic, aromatic or heterocyclic ring systems with each other.

[0394] 8. The method of any one of embodiments 1 to 7, wherein the composition further comprises another (meth)acrylate monomer different from the (meth)acrylate monomer of formula (I), preferably said other (meth)acrylate monomer is a mono-(meth)acrylate monomer, more preferably it is a mono-methacrylate monomer or a mono-acrylate monomer, and even more preferably it is represented by the following formula (II).

[0395] (II)

[0396] X 3 It is an unsubstituted or substituted alkyl, aryl, or alkoxy group;

[0397] Preferably, the symbol X 3 yes

[0398] The "*" on the left side of the equation indicates the terminal base C=CR of equation (I). 5 The connection point;

[0399] l is 0 or 1;

[0400] R 5 It is a hydrogen atom, a halogen atom that is Cl, Br or F, a methyl, alkyl, aryl, alkoxy, ester or carboxylic acid group;

[0401] R 6 It is a straight-chain alkylene or alkeneoxy group having 1 to 25 carbon atoms, preferably R. 6 It is a straight-chain alkylene or alkeneoxy group having 1 to 15 carbon atoms, more preferably 1 to 5 carbon atoms.

[0402] It can be generated by one or more groups R a Substitution, wherein one or more non-adjacent CH2 groups can be replaced by Ra C=CR a C≡C, Si(R) a )2、Ge(R a )2、Sn(R a 2. C=O, C=S, C=Se, C=NR a P(=O)(R) a SO, SO2, NR a OS or CONR a The substitution is possible, and one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2;

[0403] R 7 It is a straight-chain alkylene or alkeneoxy group having 1 to 25 carbon atoms, preferably R. 7 It is a straight-chain alkylene or alkeneoxy group having 1 to 15 carbon atoms, more preferably 1 to 5 carbon atoms.

[0404] It can be generated by one or more groups R a Substitution, wherein one or more non-adjacent CH2 groups can be replaced by R a C=CR a C≡C, Si(R) a )2、Ge(R a )2、Sn(R a 2. C=O, C=S, C=Se, C=NR a P(=O)(R) a SO, SO2, NR a OS or CONR a The substitution is possible, and one or more H atoms can be replaced by D, F, Cl, Br, I, CN or NO2;

[0405] R a Each time it appears, it is the same or different of H, D, or an alkyl group having 1 to 20 carbon atoms, a cycloalkyl or alkoxy group having 3 to 40 carbon atoms, an aromatic ring system having 5 to 60 ring carbon atoms, or a heteroaromatic ring system having 5 to 60 carbon atoms, wherein the H atom can be replaced by D, F, Cl, Br, I; two or more adjacent substituents R a They can also form monocyclic or polycyclic, aliphatic, aromatic or heterocyclic ring systems with each other.

[0406] 9. The method of any one of embodiments 1 to 8, wherein the composition contains a (meth)acrylate monomer of formula (II), wherein the mixing ratio of the (meth)acrylate monomer of formula (I) to the (meth)acrylate monomer of formula (II) is 1:99 to 99:1 (formula (I): formula (II)), preferably 5:95 to 50:50, more preferably 10:90 to 40:60, even more preferably 15:85 to 25:75, preferably using at least purified (meth)acrylate monomers represented by formulas (I) and (II) in the composition, more preferably both the (meth)acrylate monomer of formula (I) and the (meth)acrylate monomer of formula (II) are obtained or available by purification methods.

[0407] 10. The method of any one of embodiments 1 to 9, wherein the boiling point (BP) of the (meth)acrylate monomer of formula (I) and / or formula (II) is 250°C or higher, preferably the boiling point of both the (meth)acrylate monomers of formula (I) and formula (II) is 250°C or higher, more preferably in the range of 250°C to 350°C, even more preferably in the range of 280°C to 350°C, and even more preferably in the range of 300°C to 348°C.

[0408] 11. The method of any one of embodiments 1 to 10, wherein the viscosity of the composition is 35 cP or lower at room temperature, preferably in the range of 1 to 35 cP, more preferably 2 to 30 cP, and even more preferably 10 to 28 cP.

[0409] 12. The method of any one of embodiments 1 to 11, wherein the luminescent portion comprises a ligand, more preferably the luminescent portion comprises an alkyl or alkenyl ligand having 2 to 20 carbon atoms.

[0410] 13. The method of any one of embodiments 1 to 12, wherein the light-emitting portion is an organic light-emitting material and / or an inorganic light-emitting material, more preferably the organic light-emitting material is an organic dye, or an organic light-emitting material for an organic light-emitting diode device, and more preferably the inorganic light-emitting material is an inorganic phosphor and / or a quantum material.

[0411] 14. The method of any one of embodiments 1 to 13, wherein the composition further comprises one or more additional materials selected from the group consisting of:

[0412] A) Another light-emitting portion, which is different from the light-emitting portion of embodiment 1, preferably the light-emitting portion is an organic light-emitting material and / or an inorganic light-emitting material, more preferably the organic light-emitting material is an organic dye, or an organic light-emitting material for an organic light-emitting diode device, more preferably the inorganic light-emitting material is an inorganic phosphor and / or a quantum material, preferably the light-emitting portion includes a ligand, more preferably the light-emitting portion includes an alkyl or alkenyl ligand having 2 to 25 carbon atoms;

[0413] B) Another (meth)acrylate monomer; and

[0414] C) Optically transparent polymers, antioxidants, free radical quenchers, photoinitiators and / or surfactants.

[0415] 15. The method of any one of embodiments 1 to 14, wherein, based on the total amount of the composition, the composition comprises 10% by weight or less of a solvent, more preferably 5% by weight or less, more preferably a solvent-free composition, and preferably the composition does not contain any solvent selected from one or more of the group consisting of: ethylene glycol monoalkyl ethers, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; diethylene glycol dialkyl ethers, such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, and diethylene glycol dibutyl ether; propylene glycol monoalkyl ethers, such as propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, and propylene glycol monopropyl ether; ethylene glycol alkyl ether acetates, such as methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol alkyl ether acetates, such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether... Esters and propylene glycol monopropyl ether acetate; ketones, such as methyl ethyl ketone, acetone, methyl pentyl ketone, methyl isobutyl ketone, and cyclohexanone; alcohols, such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, triethylene glycol, and glycerol; esters, such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and ethyl lactate; and cyclic esters, such as γ-butyrolactone; chlorinated hydrocarbons, such as chloroform, dichloromethane, chlorobenzene, and trimethylbenzene. Examples of solvents include 1,3,5-trimethylbenzene, 1,2,4-trimethylbenzene, 1,2,3-trimethylbenzene, dodecylbenzene, cyclohexylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 3-isopropylbiphenyl, 3-methylbiphenyl, 4-methylbiphenyl, and dichlorobenzene. Preferably, the solvent is propylene glycol alkyl ether acetate, alkyl acetate, ethylene glycol monoalkyl ether, propylene glycol, and propylene glycol monoalkyl ether.

[0416] 16. A cured composition obtained or available by any one of the methods in embodiments 1 to 15.

[0417] 17. A layer obtained or available by any of the methods in implementation schemes 1 to 15.

[0418] 18. A layer comprising a light-emitting portion, a matrix material, and scattering particles, wherein, based on the total amount of the layer, the total amount of the light-emitting portion ranges from 0.1 wt% to 90 wt%, more preferably from 10 wt% to 70 wt%, and even more preferably from 30 wt% to 50 wt%; and

[0419] The total amount of scattering particles, based on the total amount of the layer, is 10% by weight or less, preferably in the range of 5% to 1% by weight, more preferably in the range of 4% to 2% by weight. The layer is preferably configured to achieve an EQE value of 20% or higher, more preferably in the range of 20% to 99%, more preferably in the range of 30% to 50%, and even more preferably in the range of 30% to 40%. For blue-green conversion efficiency, the layer is preferably a patterned layer.

[0420] 19. The layer of embodiment 17 or 18, wherein the layer thickness is in the range of 1 to 50 μm, preferably 5 to 15 μm, more preferably 8 to 15 μm, and even more preferably 8 to 12 μm.

[0421] 20. A color conversion device (100) comprising at least a first pixel (161) which is partially or completely filled with the cured composition of embodiment 16 or a layer filled with any one of embodiments 17 to 19, and a dam (150) comprising at least a polymer material, preferably, the color conversion device (100) further comprising a support medium (170).

[0422] 21. The device (100) of embodiment 20, wherein the height of the embankment (150) is in the range of 0.1 to 100 μm, preferably 1 to 50 μm, more preferably 1 to 25 μm, and even more preferably 5 to 20 μm.

[0423] 22. The device (100) of embodiment 20 or 21, wherein the layer thickness of the pixel (161) is in the range of 0.1 to 100 μm, preferably 1 to 50 μm, more preferably 5 to 25 μm.

[0424] 23. The device (100) of any one of embodiments 20 to 22, further comprising a second pixel (162), preferably, the device (100) comprising at least a first pixel (161), a second pixel (162) and a third pixel (163), more preferably, the first pixel (161) is a red pixel, the second pixel (162) is a green pixel and the third pixel (163) is a blue pixel, and even more preferably, the first pixel (161) contains a red light-emitting portion (110R), the second color pixel (162) contains a green light-emitting portion (110G) and the third pixel (163) does not contain any light-emitting portion.

[0425] 24. A device (100) according to any one of embodiments 20 to 23, wherein at least one pixel (160) further comprises at least one light scattering particle (130) in a matrix material (120), preferably, the pixel (160) comprises multiple light scattering particles (130).

[0426] 25. The device (100) of any one of embodiments 20 to 24, wherein the first pixel (161) comprises one pixel or two or more sub-pixels, the sub-pixels being configured to emit red when illuminated by excitation light, more preferably, the sub-pixels comprising the same light-emitting portion (110).

[0427] 26. The device (100) of any one of embodiments 20 to 25, wherein the dam (150) is configured to determine the area of ​​the first pixel (161), and at least a portion of the dam (150) directly contacts at least a portion of the first pixel (161), preferably, the second polymer of the dam (150) directly contacts at least a portion of the first polymer of the first pixel (161).

[0428] 27. The device (100) of any one of embodiments 20 to 26, wherein the dam (150) is photolithographically patterned and the first pixel (161) is surrounded by the dam (150), preferably, the first pixel (161), the second pixel (162) and the third pixel (163) are all surrounded by the photolithographically patterned dam (150).

[0429] 28. Use of the color conversion device (100) of any one of embodiments 20 to 27 in an optical device (300), said optical device (300) comprising at least one functional medium (320, 420, 520) configured to modulate light or configured to emit light.

[0430] 29. An optical device (300) comprising at least one functional medium (320, 420, 520) configured to modulate light or to emit light, and a color conversion device (100) of any one of embodiments 20 to 28.

[0431] Technical effects of the invention

[0432] QD inks with fewer or no TiO2 or typical scattering particles are available, thus providing greater flexibility in ink design and the selection and concentration of other ink components.

[0433] The benefits of this invention are that, compared to reference inks, it achieves higher EQE and lower BL for QD inks with no or fewer scattering particles, higher haze values ​​for cured QD inks with no or fewer scattering particles, and higher haze values ​​while simultaneously achieving higher EQE, and potentially lower blue light leakage.

[0434] A novel method for preparing cured compositions with higher EQE, lower blue light leakage, shorter process time, improved haze value after curing, improved curing to polymerize the composition, and / or achieving lower viscosity of the composition.

[0435] The goal is to find the optimal amount of luminescent components and scattering particles in the composition to achieve a composition with low viscosity, high EQE, low blue light leakage, and good inkjet performance.

[0436] The following working examples 1-15 provide a description of the invention and a detailed description of their manufacture.

[0437] Working Example

[0438] Working Example 1: Preparation of Monomer Mixtures

[0439] 1,6-Hexanediol diacrylate (HDDA) was purified by molecular sieve before use. 2 g of HDDA and 8 g of lauryl acrylate (LA, viscosity: 4.0 cP, BP: 313.2 °C) were mixed in a glass vial to obtain a monomer mixture. The weight ratio of HDDA to LA in the monomer mixture was 20:80.

[0440] Working Example 2: Preparation of QD Ink

[0441] QD Ink A is prepared by mixing the following materials.

[0442]

[0443] Working Example 3: Preparation of QD Ink

[0444] QD Ink B is prepared by mixing the following materials.

[0445]

[0446] Working Example 4: Manufacturing of QD Test Kit

[0447] The QD ink A obtained in Working Example 2 was injected into 6 test boxes with a 10mm gap.

[0448] Then, the obtained six test boxes containing QD ink A were cured by applying UV light irradiation with different curing time conditions to prepare cured ink in the test boxes.

[0449] • UV intensity: First irradiation step: 1.7 mW / cm 2

[0450] Second light irradiation step: 300 mW / cm 2

[0451] • Light source: 395nm LED (peak wavelength: 395nm)

[0452] • Under N2 conditions (O2: 0.1%)

[0453] • Curing time:

[0454]

[0455] Obtain test kits 1 through 6.

[0456] Working Example 5: Manufacturing of QD Test Kit

[0457] Test kit B was manufactured in the same manner as described in Working Example 3, except that QD ink B obtained in Working Example 3 was used instead of QD ink A.

[0458] • Curing time:

[0459]

[0460] Obtain test kits 7 to 12.

[0461] Working Example 6: EQE Measurement and Blue Light Leakage Measurement

[0462] EQE measurements were performed using an integrating sphere equipped with fiber optic excitation light (CWL: 450 nm) and a spectrometer (USB4000, OceanOptics). Air was used as a reference at room temperature to detect photons from the excitation light.

[0463] The number of photons emitted from the box to the integrating sphere is calculated using a spectrometer at room temperature.

[0464] EQE is calculated using the following method.

[0465] EQE = Photon [Emitted Light] / Photon [Excitation Light]

[0466] Calculate wavelength range

[0467] Excitation: 430 nm-470 nm

[0468] Emissions: [Green] 480 nm - 600 nm, [Red] 560 nm - 680 nm

[0469] Blue light leakage was measured using an integrating sphere equipped with fiber optic excitation light (CWL: 450 nm) and a spectrometer (USB4000, Ocean Optics). Air was used as a reference at room temperature to detect photons of the excitation light.

[0470] The number of photons emitted from the box to the integrating sphere is calculated using a spectrometer at room temperature.

[0471] Blue light leakage is calculated using the following method.

[0472] BL = Photon [Non-absorption excitation light] / Photon [excitation light]

[0473] Calculate wavelength range

[0474] Excitation: 430 nm-470 nm

[0475] Table 1 shows the results of EQE and blue light leakage (BL) measurements of the test boxes obtained in working examples 4 and 5.

[0476] Table 1:

[0477]

[0478] By applying the two-step curing method of this invention, improved EQE, shorter production time, and reduced blue light leakage are achieved simultaneously.

[0479] From the viewpoint of achieving higher EQE, it is suitable to irradiate the composition with light of lower intensity until the composition polymerizes. Preferably, the total energy of the light irradiation is about 2-3 J / cm². 2 .

[0480] Working Example 7: Manufacturing of QD Test Kit and Haze Measurement

[0481] For haze value measurement, four test boxes (QD45-1, QD45-2, QD45-3, QD45-4) were manufactured under the same conditions as described in working examples 2 and 4.

[0482] Then, four test boxes (QD45-SB-1, QD45-SB-2, QD45-SB-3, QD45-SB-4) were manufactured in the same manner as described in Examples 3 and 4.

[0483] In addition, except that 50% by weight of green QD (Merck) is used instead of 45% by weight, four test boxes (QD50-1, QD50-2, QD50-3, QD50-4) are manufactured in the same manner as described in Working Examples 2 and 4.

[0484] Finally, four test boxes (QD50-SB-1, QD50-SB-2, QD50-SB-3, QD50-SB-4) were manufactured in the same manner as described in Working Examples 3 and 4, except that 50% by weight of green QD (Merck) was used instead of 45% by weight of green QD.

[0485] The test boxes were then cured by irradiating them with the following conditions.

[0486] • Light source: 395 nm LED (peak wavelength: 395 nm)

[0487] • Under N2 conditions (O2: 0.1%)

[0488] • UV intensity: 1.7 mW / cm² for both Sample 1 and Sample 2. 2

[0489] (QD45-1, QD45-2, QD45-SB-1, QD45-SB-2, QD50-1, QD50-2, QD50-SB-1 and QD50-SB-2)

[0490] Samples 3 and 4 were 300 mW / cm 2

[0491] (QD45-3, QD45-4, QD45-SB-3, QD45-SB-4, QD50-3, QD50-4, QD50-SB-3 and QD50-SB-4)

[0492] Note: This is not a "two-step curing method".

[0493] The haze values ​​of the test samples before and after photocuring were measured at room temperature in air using a spectrometer (Shimadzu, UV-2550) equipped with an integrating sphere detector. A test chamber containing a 10 μm thick layer (liquid or cured solid) sandwiched between two 0.7 mm thick AF glasses was mounted in the beam path in front of the integrating sphere. Measurements were then performed in the 380–780 nm wavelength range using the following steps, T1 to T4, in this sequence:

[0494] (T1) All light emitted by the spectrometer light source is collected by an integrating sphere enclosed by a white reflector for measurement by the spectrometer, and the test box is not in the beam path in front of the integrating sphere;

[0495] (T2) The incident light first passes through the sample and is then collected in a closed integrating sphere to measure all the light passing through the sample. The test box is placed in the beam path in front of the integrating sphere.

[0496] (T3) Allow the incident light to pass through an open integrating sphere to determine the amount of scattered light, wherein the test box is not in the beam path of the integrating sphere;

[0497] (T4) The light first passes through the sample and is then collected by an open integrating sphere, with the test box placed in the beam path in front of the integrating sphere; in this configuration, the amount of light scattered by the sample is determined.

[0498] Then, the haze value is calculated using the following equation:

[0499] Haze value = ((T4 / T2)-(T3 / T1))*100 [%].

[0500] Table 2-7 shows the haze measurement results of the test box obtained in Working Example 7.

[0501] Table 2:

[0502]

[0503] Here, in the table, for example, 1.7mW-1 refers to the light intensity of light irradiating sample 1 (QD45-1 and QD45-SB-1), and 1.7mW-2 refers to the light intensity of light irradiating sample 2 (QD45-1 and QD45-SB-1).

[0504] Table 3:

[0505]

[0506] Table 4:

[0507]

[0508] Table 5:

[0509]

[0510] Table 6:

[0511]

[0512] Table 7:

[0513]

[0514] Working Example 8: Manufacturing of QD Test Kit

[0515] Except for using QD inks with 45 wt% and 50 wt% QD and using test kits with a 10 mm gap for manufacturing, the test kits QD45 and QD50 are manufactured in the same manner as described in working examples 2 and 4.

[0516] The test kits were then cured under different light irradiation conditions.

[0517] • Light source: 395 nm LED (peak wavelength: 395 nm)

[0518] • Under N2 conditions (O2: 0.1%)

[0519] • UV intensity: 1.7, 10, 50, 150 and 300 mW / cm 2

[0520] Working Example 9: EQE Measurement and Blue Light Leakage Measurement

[0521] Except for using the test kit obtained in Working Example 8, EQE measurements and blue light leakage measurements were performed in the same manner as described in Working Example 6.

[0522] Table 8:

[0523]

[0524] Working Example 10: Manufacturing of QD Test Kit

[0525] QD Ink C is prepared by mixing the following materials.

[0526]

[0527] The QD ink C obtained in Working Example 10 was injected into seven test boxes with a 15mm gap.

[0528] Then, as described below, each test box was cured independently under different curing conditions.

[0529] Experimental conditions

[0530] • Test sample: 15 μm test unit

[0531] • Curing conditions:

[0532] • UV dose fixed as 900 mJ / cm 2

[0533] • At N2 flow rate (0.2% O2)

[0534]

[0535] Working Example 11: Manufacturing of QD Test Kit

[0536] QD ink D was prepared in the same manner as described in Example 10, except that a monomer mixture LA+TMPTA (LA:TMPTA=90:10) was used instead of a monomer mixture LA+HDDA (LA:HDDA=80:20).

[0537] Then, the QD ink D obtained in working example 11 is injected into 7 test boxes with a 15 mm gap.

[0538] Each test box is then cured independently in the same manner as described in Working Example 10.

[0539] Working Example 12: EQE Measurement and Blue Light Leakage Measurement

[0540] In addition to using the test kits obtained in Working Examples 10 and 11, the EQE and blue light leakage measurements of the test kits obtained in Working Examples 10 and 11 are performed in the same manner as described in Working Example 6.

[0541] Figure 6 and 7 The measurement results are shown.

[0542] like Figure 6 As mentioned above, if through 300mW / cm 2 When cured by light irradiation, the EQE value obtained using QD ink C is about 5% higher than the EQE value obtained using QD ink D.

[0543] like Figure 7 As shown, if 300mW / cm 2 When cured by light irradiation, it was observed that using QD ink C resulted in approximately 8% less blue light leakage compared to using QD ink D.

[0544] Working Example 13: Manufacturing of QD Ink and Test Kit

[0545] QD load: 40, 45, 50% by weight

[0546] Titanium dioxide (scattering particles): 1, 3, 5, 7% by weight

[0547] Working Example 14: EQE Measurement and Blue Light Leakage Measurement

[0548] Except for using the test box obtained in Working Example 13, the EQE measurement of the test box is performed in the same manner as described in Working Example 6.

[0549] Figure 8 and 9 The measurement results are shown.

[0550] like Figure 8 As shown, a TiO2 loading of 3% by weight indicates the optimal EQE value.

[0551] Working Example 15: Viscosity Measurement

[0552] The viscosity of the QD ink obtained in Working Example 13 was measured at room temperature using a vibratory viscometer VM-10A (SEKONIC).

[0553] Figure 10 and 11 The measurement results are shown.

[0554] From the perspective of viscosity, EQE value and blue light leakage of QD ink composition, TiO2 loading of 3% by weight and QD loading of 45% by weight is the most suitable combination for QD ink.

Claims

1. A method for preparing a cured composition, the method comprising at least the following steps: a) Using light to irradiate the composition as the first light irradiation; b) Irradiating the composition with light as a second light irradiation; The composition comprises at least one light-emitting component, a reactive monomer, and scattering particles, wherein the light-emitting component is a semiconductor light-emitting nanoparticle; wherein the intensity of the light of the first light irradiation of step a) is in the range of 1 mW / cm 2 to 5 mW / cm 2 , the intensity of the light of the second light irradiation of step b) is in the range of 200 mW / cm 2 to 5 W / cm 2 , and the total amount of the scattering particles is in the range of 4 to 2 wt.%, based on the total amount of the solid content of the composition, The peak wavelengths of the light irradiated by the first light and the peak wavelengths of the light irradiated by the second light are independently within the range of 375 nm to 405 nm. The illumination time for the first light irradiation in step a) is in the range of 3 to 50 seconds, and the illumination time for the second light irradiation in step b) is in the range of 7 to 20 seconds. The total energy of the light irradiation is 2 J / cm². 2 Up to 3 J / cm 2 Within the range, The reactive monomers include (meth)acrylate monomers of formula (I) and (meth)acrylate monomers of formula (II), wherein the mixing ratio of the (meth)acrylate monomer of formula (I) to the (meth)acrylate monomer of formula (II) is 15:85 to 25:

75. (I) in X 1 yes ,in, The "*" on the left side of the equation indicates the terminal base C=CR of equation (I). 1 The connection point of the carbon atoms, the "*" on the right side of the formula indicates the symbol X in formula (I). 2 The connection point, n is 0 or 1, where R 3 It is a straight-chain alkylene or alkeneoxy group having 1 to 5 carbon atoms; X 2 yes In this equation, the asterisk (*) on the left side represents the symbol X in equation (I). 1 The connection point, the "*" on the right side of the equation indicates the connection with the end base C=CR of equation (I). 2 The connection point, m is 0 or 1, where R 4 It is a straight-chain alkylene or alkeneoxy group having 1 to 5 carbon atoms; R 1 It is a hydrogen atom or a methyl group; R 2 It is a hydrogen atom or a methyl group; (II) X 3 yes In this equation, the asterisk (*) on the left side indicates the terminal base C=CR of equation (II). 5 The connection point, l is 0 or 1, where R 6 It is a straight-chain alkylene or alkeneoxy group having 1 to 5 carbon atoms, R 7 It is a straight-chain alkylene or alkeneoxy group having 1 to 5 carbon atoms; R 5 It is a hydrogen atom or a methyl group.

2. The method according to claim 1, wherein the composition comprises a plurality of light-emitting components.

3. The method according to claim 1, wherein the boiling point (BP) of the (meth)acrylate monomer of formula (I) and / or formula (II) is 250°C or higher.

4. The method according to claim 1, wherein the viscosity of the composition is 35 cP or lower at room temperature.

5. The method of claim 1, wherein the composition contains 10% by weight or less solvent based on the total amount of the composition.

6. A cured composition obtained or available by the method according to claim 1.

7. A layer that is obtained or obtainable by the method according to claim 1.

8. The layer according to claim 7, comprising a light-emitting portion, a matrix material, and scattering particles, wherein the total amount of the light-emitting portion is in the range of 0.1% by weight to 90% by weight based on the total amount of the layer, and wherein the total amount of the scattering particles is in the range of 4% to 2% by weight based on the total amount of the layer.

9. The layer according to claim 7 or 8, wherein the layer thickness is in the range of 1 to 50 μm.

10. A color conversion device comprising at least a first pixel, the first pixel being partially or completely filled with a cured composition according to claim 6 or filled with a layer according to claim 7, and a dam comprising at least a polymer material.

11. An optical device comprising at least one functional medium configured to modulate light or configured to emit light, and a color conversion device according to claim 10.

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